US5670261A - Composite metal sheet and method for producing it - Google Patents
Composite metal sheet and method for producing it Download PDFInfo
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- US5670261A US5670261A US08/411,882 US41188295A US5670261A US 5670261 A US5670261 A US 5670261A US 41188295 A US41188295 A US 41188295A US 5670261 A US5670261 A US 5670261A
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- layer
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- metal sheet
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- urethane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/08—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by flames
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/145—After-treatment
- B05D3/148—After-treatment affecting the surface properties of the coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
- Y10T428/31522—Next to metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a composite metal sheet having excellent corrosion resistance, weather resistance and formability, which is composed of a metal sheet, such as a zinc-plated steel sheet, an aluminum/zinc alloy-plated steel sheet, an aluminum-plated steel sheet, an aluminum sheet, a stainless steel sheet or the like, coated with a polyolefinic thermoplastic resin and a thermosetting synthetic resin paint, and also to a method for producing such a composite metal sheet.
- a metal sheet such as a zinc-plated steel sheet, an aluminum/zinc alloy-plated steel sheet, an aluminum-plated steel sheet, an aluminum sheet, a stainless steel sheet or the like, coated with a polyolefinic thermoplastic resin and a thermosetting synthetic resin paint, and also to a method for producing such a composite metal sheet.
- Coated and surface-treated metal sheets which have heretofore been used as outdoor construction materials are produced, in general, by coating various metal sheets, such as zinc melt-plated steel sheets, electrolytic zinc-plated steel sheets, 5% Al/Zn alloy-plated steel sheets, 55% Al/Zn alloy-plated steel sheets, aluminum-plated steel sheets, aluminum sheets, stainless steel sheets, etc., by continuous coating methods, continuous film-laminating method or continuous hot-melt coating methods such as those mentioned below.
- the surfaces of various metal sheets are chemically treated, then coated with undercoat compositions and dried, and thereafter continuously coated with an adhesive layer of a modified polyolefin resin and a polyolefin resin layer by co-extruding the both resins from a T-die thereover to produce various resin-coated metal sheets.
- Coated and surface-treated metal sheets thus produced by these methods have excellent corrosion resistance, weather resistance and formability and are desirably decorated, and their quality is stabilized.
- such coated and surface-treated metal sheets do not need any posterior coating step after machined or constructed. Therefore, the use of these is broadening as materials for outdoor constructions.
- coated and surface-treated metal sheets are high weather resistance, corrosion resistance, formability and scratch resistance. Recently, however, the surroundings for outdoor constructions are being worsened, for example, by acid rain, etc., while, on the other hand, maintenance-free use of outdoor constructions is needed in such severe surroundings. Therefore, coated and surface-treated metal sheets for outdoor constructions are needed to have much more improved properties.
- the thickness of the coated layer is generally from 150 to 300 ⁇ m or so. Therefore, even though these sheets are scratched, when machined or constructed, the scratches may be within the coated layers and hardly reach the metal substrate. In addition, since these sheets are machined with ease, the machined parts are not cracked. Therefore, these sheets have excellent corrosion resistance.
- the present invention has been made in consideration of the above-mentioned problems. Its object is to provide a composite metal sheet having excellent machinability (formability), weather resistance and corrosion resistance, which could not be obtained by any of continuous coating methods, continuous film-laminating methods and hot-melt coating methods for producing various metal sheets, and also to provide a method for producing such a composite metal sheet.
- the present invention is to solve the above-mentioned problems, providing the following:
- a composite metal sheet having, on the surface of a metal substrate, a chemical-treated layer as the lowest layer, a primer layer of an organic resin-based paint thereon, a two-layered resin interlayer with a thickness of from 50 to 300 ⁇ m composed of an adhesive layer of a modified polyolefin resin and a polyolefin resin layer, the surface of said resin interlayer having been modified to have functional groups thereon in an amount of from 0.05 to 0.30 of O/C representing the ratio of the amount of oxygens in the functional groups to the amount of carbons on the surface, and a top coat layer with a thickness of from 8 to 35 ⁇ m made of an urethane-hardening polyester paint or an urethane-hardening fluorine paint, in this order.
- a method of producing a composite metal sheet comprising steps of chemically treating the surface of a metal substrate, coating and drying an organic resin-based paint thereon to form a primer layer, then forming thereon a two-layered resin interlayer composed of an adhesive layer of a modified polyolefin resin and a polyolefin resin layer at a thickness of from 50 to 300 ⁇ m, then modifying the surface of said polyolefin resin layer by flame treatment or corona discharging treatment thereby forming functional groups thereon in an amount of from 0.05 to 0.30 in terms of O/C representing the ratio of the amount of oxygens in the functional groups to the amount of carbons on the surface, and finally coating and drying an urethane-hardening polyester paint or an urethane-hardening fluorine paint at a thickness of from 8 to 35 ⁇ m to form a top coat layer.
- the metal substrate to be coated according to the present invention may be any of a zinc-plated steel sheet, an aluminum/zinc alloy-plated steel sheet, an aluminum-plated steel sheet, an aluminum sheet, a stainless steel sheet, etc.
- the surface of the metal substrate is chemically treated, by which the adhesiveness between the metal substrate and the undercoat layer is improved and, in addition, the corrosion resistance of the composite metal sheet of the invention is improved.
- phosphoric acid compounds for spraying or dipping treatment or chromic acid compounds for coating treatment are used. These compounds are suitably selected, depending on the kind of the metal substrate to be treated therewith.
- the surface of the thus chemically-treated metal substrate is coated with a primer paint and dried.
- the metal substrate to be coated is a zinc-plated steel sheet, an aluminum/zinc alloy-plated steel sheet, an aluminum-plated steel sheet or an aluminum sheet, strontium chromate or zinc chromate or a mixture of the two may be added as a rust-inhibiting pigment to the undercoat paint in an amount of from 10 to 40 parts by weight to 100 parts by weight of the resin in the composition, by which the corrosion resistance of the composite metal sheet of the invention may be improved further.
- the corrosion resistance of the composite metal sheet of the invention will be insufficient, but if it is more than 40 parts by weight, the improvement in the corrosion resistance is no more enhanced but the moisture resistance of the undercoat layer will be lowered rather unfavorably. It is recommended that the dry thickness of the undercoat layer is within the range between 1 ⁇ m and 20 ⁇ m.
- a two-layered composite film composed of an adhesive layer of a modified polyolefin resin and a polyolefin resin layer is coated over the surface of the thus-formed undercoat layer by co-extruding hot melts of the two resins from an extruder through its T-die, thus forming the two-layered resin interlayer on the metal sheet by direct coating under pressure, or alternatively, such a two-layered composite film is previously formed and wound up and the film is laminated on the undercoat layer to form the intended resin interlayer thereon.
- the adhesive layer is employed to improve the adhesion between the undercoat layer and the resin interlayer.
- a thermal stabilizer and/or an optical stabilizer are/is added to the polyolefin resin layer so as to prevent the layer from being decomposed by oxidation or ultraviolet rays.
- a top coat layer is provided on the coated metal sheet in the manner mentioned hereinafter. Therefore, since the polyolefin resin layer is not directly exposed to oxygen, ultraviolet rays, etc., the addition of such thermal stabilizer and optical stabilizer is not indispensable.
- the thickness of the two-layered resin interlayer composed of an adhesive layer of a modified polyolefin resin and a polyolefin resin layer is within the range between 50 ⁇ m and 300 ⁇ m, but the thickness is more preferably with the range between 80 ⁇ m and 300 ⁇ m.
- the thickness of the adhesive layer of a modified polyolefin resin is preferably within the range between 5 ⁇ m and 30 ⁇ m. If it is less than 5 ⁇ m, the adhesiveness between the undercoat layer and the adhesive layer will be unstable, but if it is more than 30 ⁇ m, such does not result in the increase in the adhesiveness of the layer but rather increases the cost of the product.
- polystyrene resin preferably used are a polyethylene resin, a polypropylene resin and a mixture of polyethylene and polypropylene resins.
- the thickness of the resin interlayer is less than 50 ⁇ m, the severe formability of the composite metal sheet of the invention for embossing it and so on will be poor and the sheet is defective in that the machined area of its coat is often cracked.
- the thickness of the polyolefin resin interlayer is preferably 80 ⁇ m or more is because, since polyolefin resins have excellent resistance against water penetration and moisture penetration therethrough, the interlayer is effective in protecting the metal substrate from the outdoor corroding environment when the composite metal sheet of the invention is used in the outdoors. If the thickness of the resin interlayer is less than 80 ⁇ m, there will be a great risk of being such that the scratches made on the composite metal sheet product of the invention when the sheet is machined or constructed reach the metal substrate. If so, it will be difficult to expect sufficient corrosion resistance of the composite metal sheet, even though the polyolefin resin layer has excellent resistance against water penetration and moisture penetration therethrough.
- the thickness of the resin interlayer is more than 300 ⁇ m, its characteristic of preventing scratches could not be improved so much but the workability in hot melt extrusion of the resin is rather lowered with the result that the production costs are increased.
- the flame resistance of the composite metal sheet of the invention is lowered. If the sheet is desired to be flame-resistant, antimony trioxide and a bromine-containing flame retardant may be added to the resin interlayer by which the flame resistance of the sheet is improved.
- bromine-containing flame retardant typically mentioned are tetrabromobisphenol-A, decabromobisphenyl ether, etc.
- polyolefin resins As one means to be used for evaluating the flame resistance of resins, there is known an oxygen index.
- polyolefin resins In general, polyolefin resins have an oxygen index of about 18%.
- the amounts of such antimony trioxide and bromine compound to be added are from 3 to 15 parts by weight each, to 100 parts by weight of the resin.
- the improvement in the flame resistance of the interlayer will be insufficient. If, however, they are more than 15 parts by weight, the improvement in its flame resistance will no more be enhanced but the formability of the composite metal sheet of the invention will be worsened rather defectively.
- the resin interlayer After the resin interlayer has been formed, its surface is modified by flame treatment or corona discharging treatment, by which functional groups such as hydroxyl group, carbonyl group, carboxyl group, etc. are formed on the surface of the polyolefin resin layer so that the polarity of the surface is elevated and the adhesiveness between the layer and the top coat layer to be formed thereover is improved.
- functional groups such as hydroxyl group, carbonyl group, carboxyl group, etc.
- the degree of the surface modification of the resin interlayer may be determined by analyzing the oxygen amount (O) and the carbon amount (C) on the modified surface, using ESCA (X-ray Photoelectron Spectroscopy; XPS), followed by obtaining its ratio of O/C.
- ESCA X-ray Photoelectron Spectroscopy; XPS
- the oxygen amount means the amount of oxygens to be contained in the functional groups formed by the surface modification. With the progress of the surface modification, the oxygen amount is increased, resulting in the increase in the ratio O/C.
- the matter to which the inventor has paid the best attention is to specifically determine the O/C value.
- the reason is because if the adhesiveness of the polyolefin resin layer to the top coat layer is lost while the composite metal sheet is used in the outdoors for a long period of time with the result that the top coat layer is peeled from the underlying polyolefin resin layer, then not only the quality of the sheet but also the commercial value thereof is noticeably damaged.
- the O/C value at which the adhesiveness between the two layers is stabilized is within the range between 0.05 and 0.30 just before coating the top coat layer over the polyolefin resin layer.
- the amount of the functional groups on the surface of the polyolefin resin layer is smaller than the necessary one, so that the adhesiveness between the polyolefin resin layer and the top coat layer thereon cannot be ensured satisfactorily.
- the top coat layer must be such that it is stable and durable for a long period of time when the composite metal sheet of the invention is used in the outdoors and, additionally, it reacts with the functional groups existing on the surface of the polyolefin resin layer thereby improving its adhesiveness to the underlying resin interlayer.
- polyester resin paints and fluorine resin paints of fluoro-olefin vinyl ether polymers, containing isocyanates as the crosslinking agent are preferred.
- the primary adhesiveness of the top coat layer formed to the underlying rein interlayer may be obtained but its adhesiveness is noticeably lowered after the composite metal sheet is kept wet for a long period of time.
- the coating composition for the top coat layer must contain an isocyanate compound as the crosslinking agent.
- the amount of the isocyanate compound to be used as the crosslinking agent is from 15 to 55 parts by weight to 100 parts by weight of the resin in the coating composition (paint).
- the amount of the isocyanate compound is less than 15 parts by weight, the hardness of the top coat layer itself will be low and a suitable top coat layer cannot be formed.
- the top coat layer to be formed will be too hard so that its formability is worsened, thereby causing some problems in shaping and machining the composite metal sheet.
- the thickness of the top coat layer is within the range between 8 ⁇ m and 35 ⁇ m. If the thickness of the top coat layer is less than 8 ⁇ m, ultraviolet rays will pass through the top coat layer while the composite metal sheet is used in the outdoors, thereby deteriorating the resin interlayer. As a result, there will be an unfavorable probability that the adhesiveness between the resin interlayer and the top coat layer is lowered.
- antimony trioxide and a bromine compound may be added to the resin interlayer so as to improve the flame resistance of the interlayer.
- antimony trioxide and a bromine compound may also be added to the top coat layer, thereby further improving the flame resistance of the composite metal sheet.
- the amounts of the antimony trioxide and the bromine compound to be added to the top coat layer are from 3 to 15 parts by weight each, to 100 parts by weight of the resin in the layer.
- the improvement in the flame resistance of the top coat layer will be insufficient. If, however, they are more than 15 parts by weight, the improvement in its flame resistance will no more be enhanced but the formability of the composite metal sheet of the invention will be worsened rather defectively.
- a silver-containing, inorganic anti-microbial agent may be added to the top coat layer, thereby making it resistant to microbes and fungi (mold).
- silver-containing, inorganic anti-microbial agent usable for this purpose for example, mentioned are titanium phosphate-zinc oxide-silver, zeolite-silver, apatite-silver, zirconium phosphate-silver, Apacider A of a sintered product composed of calcium phosphate and a silver compound (produced by Sangi Co.), Clean P-2-D consisting essentially of SiO 2 .Al 2 O 3 .ZnO.Li 2 O.Ag (produced by Nichihan Laboratories Co.), etc.
- Such a microbicide is added to the top coat layer in an amount of from 0.05 to 2 parts by weight to 100 parts by weight of the top-coating resin. If its amount is less than 0.05 parts by weight, the anti-bacterial and anti-fungal property of the layer will be low. However, even if its amount is more than 2 parts by weight, the anti-bacterial and anti-fungal property of the layer will be no more improved.
- Table 1 shows the manufacture conditions in Example 1 to Example 6 of the present invention.
- Table 2 shows the manufacture conditions in Comparative Example 1 to Comparative Example 7, which are similar to the method of the present invention but deviate from the conditions of the present invention.
- Table 3 shows the manufacture conditions in Comparative Example 8 to Comparative Example 12 which demonstrate the manufacture of conventional coated steel sheets.
- the top coat layer was formed without modifying the surface of the polyolefin resin layer.
- Comparative Example 2 the surface modification of the polyolefin resin layer was effected by corona discharging but the formation of the functional groups thereon was unsatisfactory. In Comparative Example 3, the formation of the functional groups on the polyolefin resin layer was excessive due to the surface modification of the layer.
- the top coat layer was made of a fluorine-containing paint which is not an urethane-curing composition.
- the top coat layer was made of a melamine-curing polyester paint.
- Comparative Example 6 the thickness of the resin interlayer is thin and 40 ⁇ m. In Comparative Example 7, the content of the rust-inhibiting pigment in the undercoat layer is low and 5%.
- Table 4 shows the manufacture conditions of examples of the present invention and comparative examples, in which additives for improving the flame resistance of the samples and additives for improving the anti-bacterial and anti-fungal properties thereof were added to the resin interlayer and the top coat layer, respectively.
- Table 5 shows the results of the test for evaluating the adhesiveness between the polyolefin resin layer and the top coat layer in the samples of Example 1 to Example 6, Example 9, Example 10, and Comparative Example 1 to Comparative Example 5.
- the adhesiveness was determined by a cross-cut tape-peeling test according to JIS K5400 and represented by the number of the squares remained without being peeled, per 100 squares tested.
- each sample was subjected to a cycle test of 10 cycles, in which one cycle comprised dipping in boiling water for 24 hours, then drying in air for 24 hours, then subjecting to the cross-cut tape-peeling test, then dipping in water at 60° C. for 20 days, then drying in air for 24 hours, then subjecting to the cross-cut tape-peeling test, then keeping at -20° C. for 8 hours and then keeping at 60° C. for 16 hours, in this order.
- each sample was subjected to the cross-cut tape-peeling test, then kept at a temperature of 50° C. and a humidity of 98% or more for 2000 hours, then dried in air for 24 hours, and then subjected to the final cross-cut tape-peeling test.
- Table 6 shows the results of the tests for evaluating various film properties of the samples of Example 1 to Example 6, Example 9, Example 10, Comparative Example 6, Comparative Example 7, and Comparative Examples 8 to 12 for the prior art.
- the corrosion resistance was determined by a salt spraying test according to JIS Z2700, in which salt spraying was effected for 3000 hours. Before the test, each sample was treated in the manner mentioned below to make a 0T-bent area and a scratched area. After the test, the flat area, the 0T-bent area and the scratched area in each sample were checked as to whether or not they were corroded.
- the weather resistance was determined by a sun shine weather meter test according to JIS K5400, in which each sample was exposed for 3000 hours. After thus exposed, the color difference between the sample and the standard sheet and the percentage of the gloss retention of the surface of each sample were measured.
- the formability was determined by a bending test for adhesiveness and a Du Pont impact strength test.
- the sample of Comparative Example 13 contained no flame retardant.
- the sample of Comparative Example 14 contained flame retardants in both the resin interlayer and the top coat layer but their amounts were not sufficient.
- bacteria Escherichia coli
- bacteria Staphylococcus aureus
- the sample of Comparative Example 13 contained no anti-bacterial and anti-fungal agent.
- the sample of Comparative Example 15 contained an anti-bacterial and anti-fungal agent in the top coat layer but its amount was not sufficient.
- the composite metal sheet of the present invention since the composite metal sheet of the present invention has a top coat layer made of an urethane-curing polyester resin composition or an urethane-curing fluorine-containing resin composition on the interlayer made of a polyolefin resin composition, it has extremely excellent corrosion resistance due to the intrinsic characteristics of the polyolefin resin of being resistant to water penetration and moisture penetration.
- the top coat layer may protect the interlayer from ultraviolet rays.
- the top coat layer has excellent weather resistance.
- the composite metal sheet of the present invention has much more excellent durability than other coated metal sheets to be obtained by conventional continuous coating methods, continuous laminating methods or continuous hot melt-coating methods.
- the composite metal sheet having such excellent weather resistance and corrosion resistance may additionally have excellent anti-bacterial and anti-fungal properties.
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- Wood Science & Technology (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
TABLE 1 (1) __________________________________________________________________________ Manufacture Conditions in Examples of the Invention Composition for undercoat Layer Metal Substrate Kind Drying Drying Thickness Chemical (content of rust- Thickness Temperature Time Example Kind (mm) Treatment inhibiting pigment) (μ) (°C.) (sec) Resin Interlayer __________________________________________________________________________ 1 zinc-plated 0.27 zinc epoxy (20%) 5 200 40 adhesive layer Steel sheet phosphate, polyolefin layer sprayed 2 5% Al/Zn 0.80 chromate, urethane-modified 7 190 60 adhesive layer alloy-plated coated epoxy (15%) polyolefin layer steel sheet 3 5% Al/Zn 0.35 chromate, epoxy (25%) 4 210 40 adhesive layer alloy-plated coated polyolefin layer steel sheet 4 55% Al/Zn 0.40 chromate, epoxy (35%) 20 200 50 adhesive layer alloy-plated coated polyolefin layer steel sheet 5 aluminum 0.60 chromate, urethane-modified 2 190 50 adhesive layer sheet coated epoxy (30%) polyolefin layer 6 stainless steel 0.60 chromate, epoxy (10%) 3 210 50 adhesive layer sheet coated polyolefin __________________________________________________________________________ layer
TABLE 1(2) __________________________________________________________________________ Manufacture Conditions in Examples of the Invention Coating Composition for Top Coat Layer Resin Interlayer Drying Drying Thickness Coating Surface Modification Kind Thickness Temperature Time Example Kind (μ) Method Kind O/C Value (color) (μ) (°C.) (sec) __________________________________________________________________________ 1 modified 5 direct co- flame 0.12 urethane- 12 230 50 polyethylene extrusion treatment curing polyethylene 80 through T-die polyester (green) 2 modified 5 lamination of corona 0.18 urethane- 25 210 70 polyethylene two-layered discharging curing polypropylene 50 film treatment fluorine resin (blue) 3 modified 10 direct co- flame 0.25 urethane- 20 230 50 polyethylene extrusion treatment curing mixture of 150 through T-die polyester polyethylene (beige) and polypropylene 4 modified 30 direct co- flame 0.07 urethane- 18 220 60 polyethylene extrusion treatment curing polyethylene 130 through T-die polyester (gray) 5 modified 15 lamination of corona 0.10 urethane- 18 220 60 polyethylene two-layered discharging curing polypropylene 280 film treatment fluorine resin (cream) 6 modified 20 direct co- flame 0.28 urethane- 22 220 60 polyethylene extrusion treatment curing mixture of 180 through T-die fluorine resin polyethylene (brown) and polypropylene __________________________________________________________________________
TABLE 2 (1) __________________________________________________________________________ Manufacture Conditions in Comparative Examples Composition for undercoat Layer Metal Substrate Kind Drying Drying Comparative Thickness Chemical (content of rust- Thickness Temperature Time Example Kind (mm) Treatment inhibiting pigment) (μ) (°C.) (sec) Resin Interlayer __________________________________________________________________________ 1 zinc-plated 0.50 zinc epoxy (28%) 8 200 40 adhesive layer steel sheet phosphate, polyolefin layer sprayed 2 5% Al/Zn 0.80 chromate, urethane-modified 18 190 60 adhesive layer alloy-plated coated epoxy (25%) polyolefin layer steel sheet 3 5% Al/Zn 0.60 chromate, epoxy (28%) 7 190 50 adhesive layer alloy-plated coated polyolefin layer steel sheet 4 aluminum 0.60 chromate, epoxy (12%) 5 190 50 adhesive layer sheet coated polyolefin layer 5 5% Al/Zn 0.80 chromate, urethane-modified 10 190 60 adhesive layer alloy-plated coated epoxy (35%) polyolefin layer steel sheet 6 zinc-plated 0.35 zinc epoxy (30%) 3 200 40 adhesive layer steel sheet phosphate, polyolefin layer sprayed 7 5% Al/Zn 0.80 chromate, urethane-modified 5 190 60 adhesive layer alloy-plated coated epoxy (5%) polyolefin layer steel sheet __________________________________________________________________________ *: outside the scope of the present invention.
TABLE 2(2) __________________________________________________________________________ Manufacture Conditions in Comparative Examples Coating Composition for Top Coat Layer Resin Interlayer Drying Drying Comparative Thickness Coating Surface Modification Kind Thickness Temperature Time Example Kind (μ) Method Kind O/C Value (color) (μ) (°C.) (sec) __________________________________________________________________________ 1 modified 10 direct co- not surface- 0.01 urethane- 20 230 50 polyethylene extrusion modified* curing polyethylene 100 through T-die polyester (ivory) 2 modified 8 lamination of corona 0.04* urethane- 15 230 70 polyethylene two-layered discharging curing polypropylene 250 film treatment polyester (gray) 3 modified 30 direct co- flame 0.04* urethane- 18 220 60 polyethylene extrusion treatment curing polyethylene 150 through T-die polyester (brown) 4 modified 10 direct co- flame 0.25 thermoplastic 22 250 60 polyethylene extrusion treatment acrylic- polyethylene 150 through T-die modified fluorine resin* (green) 5 modified 15 lamination of corona 0.18 melamine- 15 230 70 polyethylene two-layered discharging curing polypropylene 250 film treatment polyester* (blue) 6 modified 10 direct co- flame 0.25 urethane- 15 210 50 polyethylene extrusion treatment curing polyethylene 30* through T-die fluorine resin (white) 7 modified 15 lamination of corona 0.18 urethane- 15 230 70 polyethylene two-layered discharging curing polypropylene 90 film treatment polyester (beige) __________________________________________________________________________ *: outside the scope of the present invention.
TABLE 3(1) __________________________________________________________________________ Manufacture Condition for Conventional Coated Steel Sheets Composition for undercoat Layer Kind Metal Substrate (content of rust- Drying Comparative Thickness Chemical inhibitng Temperature Drying Time Example Kind (mm) Treatment pigment) Thickness (μ) (°C.) (sec) __________________________________________________________________________ 8 zinc-plated 0.35 zinc epoxy 5 200 30 steel sheet phosphate, (35%) sprayed 9 5% Al/Zn 0.60 chromate, epoxy 7 190 50 alloy-plated coated (20%) steel sheet 10 55% Al/Zn 0.50 chromate, epoxy 5 200 50 alloy-plated coated (40%) steel sheet 11 zinc-plated 0.40 zinc epoxy- 4 180 60 steel sheet phosphate, modified sprayed acryl (28%) 12 5% Al/Zn 0.40 chromate, epoxy 5 200 50 alloy-plated coated (30%) steel sheet __________________________________________________________________________
TABLE 3(2) __________________________________________________________________________ Manufacture Conditions for Conventional Coated Steel Sheets Adhesive Coating Paint for Top Coat Layer Kind Drying Comparative (coating Kind Coating Temperature Drying Time Example system) Thickness (μ) (color) Method Thickness (μ) (°C.) (sec) __________________________________________________________________________ 8 melamine- roll coater 12 220 40 curing polyester (green) 9 vinylidene roll coater 20 245 60 fluoride- based fluorine resin (gray) 10 vinylidene roll coater 22 245 60 fluoride- based fluorine resin (cream) 11 polyvinyl roll coater 180 220 80 chloride sol (blue) 12 urethane 15 polyvinyl film 150 200 60 (roll coater) chloride film lamination (brown) __________________________________________________________________________
TABLE 4(1) __________________________________________________________________________ Manufacture Conditions for Additive-Containing Samples Resin Interlayer Kind and Amount of Additive, Thickness Example Section Kind if any (μ) Coating Method __________________________________________________________________________ 7 adhesive layer modified polyethylene antimony trioxide (8%) + 8 direct co- polyolefin layer polyethylene tetrabromobisphenol A (12%) 110 extrusion through T-die 8 adhesive layer modified polyethylene antimony trioxide (5%) + 12 lamination of polyolefin layer polypropylene decabromobisphenyl ether (8%) 120 two-layered film 9 adhesive layer modified polyethylene antimony trioxide (9%) + 15 lamination of polyolefin layer polypropylene tetrabromobisphenol A (6%) 130 two-layered film 10 adhesive layer modified polyethylene none 10 direct co- polyolefin layer mixture of polyethylene 150 extrusion and polypropylene through T-die 11 adhesive layer modified polyethylene none 25 direct co- polyolefin layer polyethylene 200 extrusion through T-die __________________________________________________________________________
TABLE 4(2) __________________________________________________________________________ Manufacture Conditions for Additive-Containing Samples Coating Paint for Top Coat Layer Surface Modification Kind Kind and Amount of Additive, Thickness Drying Drying Time Example Kind O/C Value (color) if any (μ) Temperature (°C.) (sec) __________________________________________________________________________ 7 flame 0.15 urethane-curing polyester none 15 230 70 treatment (brown) 8 corona 0.07 urethane-curing polyester antimony trioxide (7%) + 18 230 70 discharging (beige) decabromobisphenyl ether (7%) treatment 9 corona 0.18 urethane-curing fluorine antimony trioxide (14%) + 20 210 70 discharging resin (blue) tetrabromobisphenol A (12%) treatment 10 flame 0.25 urthane-curing polyester Clean P-2-D (produced by 20 230 70 treatment (gray) Nichihan Laboratories Co.) (0.1%) 11 flame 0.28 urethane-curing fluorine Apacider A (produced by Sangi 18.) 220 70 treatment resin (blue) (1.5%) __________________________________________________________________________
TABLE 4(3) __________________________________________________________________________ Manufacture Conditions for Additive-Containing Samples Resin Interlayer Comparative Kind and Amount of Additive, Thickness Coating Example Section Kind if any (μ) Method __________________________________________________________________________ 13 adhesive layer modified polyethylene none 10 direct co- polyolefin layer polyethylene 140 extrusion through T-die 14 adhesive layer modified polyethylene antimony trioxide (2%) + 8 lamination of polyolefin layer polypropylene tetrabromobisphenol A (1%) 120 two layered film 15 adhesive layer modified polyethylene 10 direct co- polyolefin layer polyethylene 180 extrusion through T-die __________________________________________________________________________
TABLE 4(4) __________________________________________________________________________ Manufacture Conditions for Additive-Containing Samples Coating Paint for Top Coat Layer Comparative Surface Modification Kind Kind and Amount of Additive, Thickness Drying Drying Time Example Kind O/C Value (color) if any (μ) Temperature (°C.) (sec) __________________________________________________________________________ 13 flame 0.11 urethane-curing polyester none 12 230 70 treatment (ivory) 14 corona 0.22 urethane-curing polyester antimony trioxide (2%) + 15 230 70 discharging (brown) decabromobisphenyl ether (2%) treatment 15 corona 0.08 urethane-curing polyester zeolite-silver (0.03%) 20 230 70 discharging (ivory) treatment __________________________________________________________________________
TABLE 5(1) __________________________________________________________________________ Evaluation of Adhesiveness O/C Value Secondary Adhesiveness after Surface Primary dipped in boiling dipped in hot after 10 wetting test for Example Modification Kind of Top Coat Film Adhesiveness water for 24 hours water for 20 days cycles 2000 __________________________________________________________________________ hours 1 0.12 urethane-curing polyester 100/100 100/100 100/100 100/100 100/100 2 0.18 urethane-curing 100/100 100/100 100/100 100/100 100/100 fluorine resin 3 0.25 urethane-curing polyester 100/100 100/100 100/100 100/100 100/100 4 0.07 urethane-curing polyester 100/100 100/100 100/100 100/100 100/100 5 0.10 urethane-curing 100/100 100/100 100/100 100/100 100/100 fluorine resin 6 0.28 urethane-curing 100/100 100/100 100/100 100/100 100/100 fluorine resin 9 0.18 urethane-curing 100/100 100/100 100/100 100/100 100/100 fluorine resin 10 0.25 urethane-curing polyester 100/100 100/100 100/100 100/100 100/100 __________________________________________________________________________
TABLE 5(2) __________________________________________________________________________ Evaluation of Adhesiveness Com- O/C Value Secondary Adhesiveness parative after Surface Primary dipped in boiling dipped in hot after 10 wetting test for Example Modification Kind of Top Coat Film Adhesiveness water for 24 hours water for 20 days cycles 2000 __________________________________________________________________________ hours 1 0.01 urethane-curing polyester 0/100 0/100 0/100 0/100 0/100 2 0.04 urethane-curing polyester 100/100 12/100 80/100 40/100 18/100 3 0.40 urethane-curing polyester 100/100 36/100 88/100 96/100 22/100 4 0.25 thermoplastic acryl- 100/100 12/100 70/100 40/100 32/100 modified fluorine resin 5 0.18 melamine-curing 100/100 80/100 92/100 80/100 60/100 polyester __________________________________________________________________________
TABLE 6 __________________________________________________________________________ Evaluation of Various Properties of Film Weather Resistance Corrosion Resistance color percentage of scratched difference gloss Machinability Color flat area OT-bent area area (ΔE) retention OT bending DuPont __________________________________________________________________________ Example 1 green good good good 3.8 68% good good Example 2 blue good good good 2.0 83% slightly goodked Example 3 beige good good good 4.5 77% good good Example 4 gray good good good 3.9 64% good good Example 5 cream good good good 1.6 90% good good Example 6 brown good good good 1.8 85% good good Example 9 blue good good good 2.2 88% good good Example 10 gray good good good 3.0 67% good good Comparative cream good good white rust 40% 1.9 84% good good Example 6 Comparative blue good good white rust 10% 3.6 60% good good Example 7 Comparative green white rust 60% white rust 100% white rust 100% 11.5 15% greatly cracked greatly cracked Example 8 Comparative gray slightly swollen white rust 40% white rust 60% 1.4 88% lightly cracked good Example 9 Comparative cream slightly swollen white rust 20% white rust 40% 1.8 86% slightly goodked Example 10 Comparative blue good lightly swollen good 10.4 10% good good Example 11 Comparative brown good slightly swollen good 12.9 6% good good Example 12 __________________________________________________________________________
TABLE 7 __________________________________________________________________________ Results of Tests for Evaluating Flame Resistance of Flame Retardant-Containing Samples Incorporation of Flame Retardant Amount of Flame Retardant in Amount of Flame Retardant Resin Interlayer in Top Coat Layer Bromine- Bromine- Results of Firing Test containing containing Exhaust After Flame Antimony Flame Antimony Flame Flame Factor Temperature Time Trioxide Retardant Trioxide Retardant (CA) (tδ⊖) (sec) __________________________________________________________________________ Example 7 8% 12% 0% 0% 10 0 15 Example 8 5% 8% 7% 7% 8 0 0 Example 9 9% 6% 14% 12% 3 0 0 Comparative 0%* 0%* 0% 0% 23 80 120 Example 13 Comparative 2% 1% 2% 2% 20 45 37 Example 14 __________________________________________________________________________ *: outside the scope of the present invention
TABLE 8 __________________________________________________________________________ Results of Tests for Anti-bacterial and Anti-fungal Properties of Samples Containing Anti-bacterial Anti-fungal Agent Amount of Anti- bacterial and Anti- fungal Agent in Results of Anti-bacterial Test Results of Anti-fungal Test Top Coat Layer Escherichia coli Staphylococcus aureus black mold blue mold __________________________________________________________________________ Example 10 0.1% not detected not detected not more than 10 not more than 10 Example 11 1.5% not detected not detected not more than 10 not more than 10 Comparative 0%* 3 × 10.sup.5 2 × 10.sup.5 much grown much grown Example 13 Comparative 0.03%* 1 × 10.sup.4 2 × 10.sup.4 3 × 10.sup.3 6 × 10.sup.2 Example 15 __________________________________________________________________________ *: outside the scope of the present invention
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6-222727 | 1994-08-25 | ||
JP22272794A JP3228022B2 (en) | 1994-08-25 | 1994-08-25 | Composite metal plate and method of manufacturing the same |
Publications (1)
Publication Number | Publication Date |
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US5670261A true US5670261A (en) | 1997-09-23 |
Family
ID=16786958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US08/411,882 Expired - Lifetime US5670261A (en) | 1994-08-25 | 1995-03-28 | Composite metal sheet and method for producing it |
Country Status (8)
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US (1) | US5670261A (en) |
EP (1) | EP0698484B1 (en) |
JP (1) | JP3228022B2 (en) |
KR (1) | KR100310962B1 (en) |
AU (1) | AU694989B2 (en) |
CA (1) | CA2146621C (en) |
DE (1) | DE69518044T2 (en) |
FI (1) | FI112047B (en) |
Cited By (14)
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WO2000030766A1 (en) * | 1998-11-25 | 2000-06-02 | Surfcoat Co., Ltd. | Printing or coating method and printing or coating device |
US6235399B1 (en) * | 1994-12-29 | 2001-05-22 | Toyo Kohan Co., Ltd. | Resin-coated metal sheet with higher vivid reflectivity having the excellent workable adhesion strength |
WO2002040180A1 (en) * | 2000-11-15 | 2002-05-23 | Ssw Holding Company, Inc. | Coating with anti-microbial agent for refrigerator shelving |
WO2002087340A1 (en) * | 2001-04-30 | 2002-11-07 | Ak Properties, Inc. | Antimicrobial coated metal sheet |
US20060150549A1 (en) * | 2005-01-13 | 2006-07-13 | Webb Alan C | Environmentally resilient corrugated building products and methods of manufacture |
US20070184201A1 (en) * | 2003-06-18 | 2007-08-09 | Ford Global Technologies Llc | Environmentally friendly reactive fixture to allow localized surface engineering for improved adhesion to coated and non-coated substrates |
US20080026316A1 (en) * | 2006-07-25 | 2008-01-31 | Endicott Interconnect Technologies, Inc. | Photoresist composition with antibacterial agent |
US20080317962A1 (en) * | 2007-03-05 | 2008-12-25 | Scott Hayes | Multi-layer and composite corrosion resistant coatings |
US20090155604A1 (en) * | 2005-09-21 | 2009-06-18 | Ford Global Technologies, Llc | Method of coating a substrate for adhesive bonding |
US20090263672A1 (en) * | 2000-01-24 | 2009-10-22 | Sinsel John A | Methods and apparatus for production of composite-coated rigid flat-rolled sheet metal substrate |
US20100151236A1 (en) * | 2008-12-11 | 2010-06-17 | Ford Global Technologies, Llc | Surface treatment for polymeric part adhesion |
US20130298469A1 (en) * | 2012-05-08 | 2013-11-14 | Guardian Industries Corp., | Silanol-inclusive adhesives, articles including components bonded to one another using silanol-inclusive adhesives, and/or associated methods |
WO2014210575A1 (en) * | 2013-06-27 | 2014-12-31 | Culpepper Taylor C | Antimicrobial devices comprising hyper-conductive and dielectric layers |
US9422459B2 (en) | 2011-07-27 | 2016-08-23 | Northrop Grumman Systems Corporation | Coatings for protection against corrosion in adhesively bonded steel joints |
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JP5214838B2 (en) * | 2003-08-21 | 2013-06-19 | 株式会社エー・エム・ティー・研究所 | Laminated body and method for producing the same |
JP4654089B2 (en) * | 2004-12-03 | 2011-03-16 | 新日本製鐵株式会社 | Chromate-free resin composite vibration damping material with excellent durability adhesion |
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JPS63165134A (en) * | 1986-12-26 | 1988-07-08 | 川鉄鋼板株式会社 | Polyolefine laminate |
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JP3094311B2 (en) * | 1992-02-12 | 2000-10-03 | 三菱化学株式会社 | Fluorine resin coated metal laminate |
JP2671718B2 (en) * | 1992-06-12 | 1997-10-29 | 大洋製鋼 株式会社 | Highly durable surface-treated metal plate and method for producing the same |
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- 1994-08-25 JP JP22272794A patent/JP3228022B2/en not_active Expired - Fee Related
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1995
- 1995-03-28 US US08/411,882 patent/US5670261A/en not_active Expired - Lifetime
- 1995-04-07 CA CA002146621A patent/CA2146621C/en not_active Expired - Fee Related
- 1995-04-18 EP EP95302532A patent/EP0698484B1/en not_active Expired - Lifetime
- 1995-04-18 DE DE69518044T patent/DE69518044T2/en not_active Expired - Fee Related
- 1995-05-31 AU AU20426/95A patent/AU694989B2/en not_active Ceased
- 1995-07-24 FI FI953550A patent/FI112047B/en active
- 1995-07-31 KR KR1019950023409A patent/KR100310962B1/en not_active IP Right Cessation
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US4888244A (en) * | 1985-09-10 | 1989-12-19 | Kansai Paint Co., Ltd. | Process for forming composite coated film |
JPS63165134A (en) * | 1986-12-26 | 1988-07-08 | 川鉄鋼板株式会社 | Polyolefine laminate |
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US6235399B1 (en) * | 1994-12-29 | 2001-05-22 | Toyo Kohan Co., Ltd. | Resin-coated metal sheet with higher vivid reflectivity having the excellent workable adhesion strength |
US6383649B2 (en) | 1994-12-29 | 2002-05-07 | Toyo Kohan Co., Ltd. | Resin-coated metal sheet with high reflectivity and excellent adhesion strength |
US6578474B1 (en) | 1998-11-25 | 2003-06-17 | Surfcoat Co., Ltd. | Printing or coating method and printing or coating device |
WO2000030766A1 (en) * | 1998-11-25 | 2000-06-02 | Surfcoat Co., Ltd. | Printing or coating method and printing or coating device |
US20090263672A1 (en) * | 2000-01-24 | 2009-10-22 | Sinsel John A | Methods and apparatus for production of composite-coated rigid flat-rolled sheet metal substrate |
WO2002040180A1 (en) * | 2000-11-15 | 2002-05-23 | Ssw Holding Company, Inc. | Coating with anti-microbial agent for refrigerator shelving |
US7026018B2 (en) * | 2000-11-15 | 2006-04-11 | Sslo Holding Company, Inc. | Coating with anti-microbial agent for refrigerator shelving |
WO2002087340A1 (en) * | 2001-04-30 | 2002-11-07 | Ak Properties, Inc. | Antimicrobial coated metal sheet |
US6929705B2 (en) | 2001-04-30 | 2005-08-16 | Ak Steel Corporation | Antimicrobial coated metal sheet |
US8586149B2 (en) | 2003-06-18 | 2013-11-19 | Ford Global Technologies, Llc | Environmentally friendly reactive fixture to allow localized surface engineering for improved adhesion to coated and non-coated substrates |
US20070184201A1 (en) * | 2003-06-18 | 2007-08-09 | Ford Global Technologies Llc | Environmentally friendly reactive fixture to allow localized surface engineering for improved adhesion to coated and non-coated substrates |
US20060150549A1 (en) * | 2005-01-13 | 2006-07-13 | Webb Alan C | Environmentally resilient corrugated building products and methods of manufacture |
US8322012B2 (en) | 2005-01-13 | 2012-12-04 | Webb Alan C | Method of manufacturing an environmentally resilient structural panel |
US8323778B2 (en) | 2005-01-13 | 2012-12-04 | Webb Alan C | Environmentally resilient corrugated building products and methods of manufacture |
US20090155604A1 (en) * | 2005-09-21 | 2009-06-18 | Ford Global Technologies, Llc | Method of coating a substrate for adhesive bonding |
US8048530B2 (en) | 2005-09-21 | 2011-11-01 | Ford Global Technologies, Llc | Method of coating a substrate for adhesive bonding |
US20080026316A1 (en) * | 2006-07-25 | 2008-01-31 | Endicott Interconnect Technologies, Inc. | Photoresist composition with antibacterial agent |
US7635552B2 (en) * | 2006-07-25 | 2009-12-22 | Endicott Interconnect Technologies, Inc. | Photoresist composition with antibacterial agent |
US20080317962A1 (en) * | 2007-03-05 | 2008-12-25 | Scott Hayes | Multi-layer and composite corrosion resistant coatings |
US20100151236A1 (en) * | 2008-12-11 | 2010-06-17 | Ford Global Technologies, Llc | Surface treatment for polymeric part adhesion |
US9422459B2 (en) | 2011-07-27 | 2016-08-23 | Northrop Grumman Systems Corporation | Coatings for protection against corrosion in adhesively bonded steel joints |
US20130298469A1 (en) * | 2012-05-08 | 2013-11-14 | Guardian Industries Corp., | Silanol-inclusive adhesives, articles including components bonded to one another using silanol-inclusive adhesives, and/or associated methods |
WO2014210575A1 (en) * | 2013-06-27 | 2014-12-31 | Culpepper Taylor C | Antimicrobial devices comprising hyper-conductive and dielectric layers |
Also Published As
Publication number | Publication date |
---|---|
DE69518044T2 (en) | 2001-03-22 |
FI953550A (en) | 1996-02-26 |
JPH0857417A (en) | 1996-03-05 |
EP0698484A2 (en) | 1996-02-28 |
KR960007823A (en) | 1996-03-22 |
AU2042695A (en) | 1996-03-07 |
FI112047B (en) | 2003-10-31 |
FI953550A0 (en) | 1995-07-24 |
DE69518044D1 (en) | 2000-08-24 |
CA2146621A1 (en) | 1996-02-26 |
EP0698484B1 (en) | 2000-07-19 |
CA2146621C (en) | 2003-01-28 |
AU694989B2 (en) | 1998-08-06 |
KR100310962B1 (en) | 2002-07-02 |
JP3228022B2 (en) | 2001-11-12 |
EP0698484A3 (en) | 1996-06-19 |
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